Vat dyestuffs of the z-thionaphthene-z-indolindigo series



Patented Jan. 4, 1927. i

UNITED STATES PATENT OFFICE.

RICHARD HERZ, OF FRANKFURT-ON-THE-MAIN, AND JENS M'U'LLER, OF HANAU-ON- THE-MAIN, GERMANY, ASSIGNORS TO GRASSELLI DYESTUFF CORPORATION, 01? NEW YORK, N. Y., A CORPORATION OF DELAWARE.

VAT DYESTUFFS OF THE 2-THIONAPHTHENE-2-INDOLINDIGO SERIES.

No Drawing. Application filed March 23, 1928, Serial No. 96,864, and in Germany October 25, 1924.

Our invention has for its object new and The dyestuffs, thus obtained, may be furvaluable dyestuffs of the 2-thionaphthene-2- ther halogenized by treating them with indolindigo series, having probably the genhalogenizing agents in the usual manner in 60 eral formula: suitable solvents or diluents.

5 Besides the perinaphthoxypenthiophene X X itself derivatives therefrom, containing sub- 0 stituents in the naphthalene nucleus may be 3 If t 5-11 "'Lv X C\ usec or ins ance or c1 oropermapi o= 2 j R thoxypenthiophene, Q-amrnoor Q-acylt; amlnoor 2-acylamino-6-bromo-perinaph- H thoxypenthiophene or i-acetylaminoperinaphthoxypenthiophene. Dyestuffs, containing the acylaminogroup in 2-position, that is 60 wherein the Xs stand for hyd g n atoms, in ortho-position to the S-atom of the side of which one 01' Ip I'Q may be rep y a chain, generally dye blue shades, but if the monovalent substituent. R means an arylacylgmup i ht ff b o ifi vtion, the residue of the benzene or naphthalene series, h d turns generally t g which may contain further substituents, Wh th m t i 1thj i di d 66 which dyestuffs dye cotton and wool from fl d i d f i hth thi the hydrosulfite vat fast blue to green shades. phene d it d i ti os ss in ufficient cco ding to ou invention p -p atlinity to the fibre, the dyestuffs produced thoXypenthiophenes 0f the general formula: according to our invention are distinguished by their good aflinity to the vegetable and To animal fibre and by their excellent fastness to light.

The materials, dyed with the new dye stuffs, also form a part of our invention.

The following examples illustrate our in- Y6 vention, the parts being by weight and all temperatures in centigrade degrees.

wherein the Xs stand for hydrogen atoms, Example of which one or more may be replaced by a 80 monovalent substituent, are condensed with 65 parts of ildichlol-Oisatin are an a-isatin compound of the general formula: pended in b t 150 parts f hlorobenzene and converted into the 4.7-dicl1l0ro-a-isatin- CO chloride by treating it in the usual manner Y with 6.5 parts of phosphorous pentachloride. R1-C R (2) The solution, thus obtained, is mined at 40 an ordinary temperature with a solution of N 6 parts of perinaphthoxypenthiophene in (I) about the tenfold quantity of chlorobenzene.

The formation of the dyestuff begins already wherein R is an arylresidue of the benzene i th ld d i l r t d b a i on or naphthalene series, which may contain the water-bath. After termination of the further substituents, R, a halogen or an reaction the formed dyestuff is filtered, arylidogroup. Washed and dried. r

The dyestufi', having probably the formula is, when dry, a dark blue powder, soluble in concentrated sulfuric acid to a blue solution.

It forms with alkaline hydrosulfite a brown-- ish colored vat and dyes cotton and wool full blue shades. The dyeings are distinguishedby avery good fast-noes to washing, milling, light and chlorine.

The reactions described above can be represented by the following formulae:

Similar blue dyeing dyestuiis are formed by substituting the l.7dichloroisatinchloride by 426- and 5.7-dichloroor LSb-trichloroisatinchloride or by l-chloro-T -metho1-:yisatinchloride or by 5-cl1loro-7-methylisatinchloride.

Instead of the a-ClllOlldG the a-arylides of these isatinbodies may be used, yielding the same good result.

Example 2.

39 parts of: l-chloro-2-3-naphthisatin-a- (l-chloro-Q) -naphthalide, produced accord ing to U. S. A. Letters Patent No. 1,083,518, are mixed with about 600 parts of acetic acid anhydride or glacial acetic acid, then 20 parts oi":perinaphthoxypenthiophene are added, andthe mixture is heated to. boiling for a short while.

The formed dyestutf is filtered, when cold, washed and dried The dyestuii, having probably the formula:

is, when dry, a dark powder, dissolving in concentrated sulfuric acid with a grey'green color, and dyes cotton and wool in the hydrosultite vat fast pure bluish green shades.

By substituting the l-chloro-EliE-naphthisatin-a(1-chloro+2) -napthalide by the equivalent quantity of bromo-1chlor0-2.3-1mphthi- (1) Formation of the 4-7-dichloro-alphaisatine chloride 54 I 6 2 e=o+ro15 7 i 0&0 4

(2) Condensation and formation of the dyestutl satin-a-(l-cl1loro-2) -11aphthalide, produced according; to U. S. A. Letters Patent No. 1,083,518, a yellow-green dyeing dyestuii is obtained. Also in this case instead of the a-na-phthalides the corresponding a-(fllllOllflGS of the halogenized 2.3-napl'1thisatin may be used.

NHCOCH3 E is when dry a blue powder, soluble in concentrated sulfuric acid to a blue solution, and dyes cotton and Wool in an orange colored hydrosulfite vat dark blue shades.

In order to split otl the acetylgroup, 5

parts of the dyestufl are dissolved in about 150-200 parts of concentrated sulfuric acid, then ice is added, until a sulfuric acid of 50% strength is formed, and the mixture is boiled under reflux for some time. After cooling down the mass is diluted with water, the separated dyestutf is filtered, washed and dried.

The saponified dyestufi', having probably the formula:

o 1 (ea s \1 NH, dyes cotton and wool in the hydrosulfite vat fast pure green shades.

Similar dyestuffs are obtained by substituting the trichloroisatinchloride by the achlorides or a-arylides of 5.7- or eff-dichloroisatin or of 4-chloro-7-n1ethoxy-isatin.

Example ,4.

39 parts of 1-chloro-2.3-naphthisatin-a- (1-chloro-2) -naphthalide are mixed with about the twentyfold quantity of glacial acetic acid, then 26 parts of 2-acetylamino perinaphthoxypenthiophene are added, the mixture is warmed slowly and finally boiled for some hours while stirring.

The solution turns at first green, then brownish red, while the product of condensation separates. It is filtered in the warm, washed and dried.

The dyestufi', having probably the formula:

NIL-COCH:

acetylaminoperinaphthoxypenthiophene with a 1-chloro-2.3-naphthisatin compound, also green dyeing dyestuffs are formed, by using 4 acetylaminoperinaphthoxypenthiophene for the condensation, a dark blue dyeing dyestuif is obtained. lVhen in the latter dyestufi' the acetylgroup is split off by saponification, fuller blue shades are obtained.

The term "penthiophene for the purpose of the present invention, and as used in the appended claims, is intended to define abody having the ring structure indicated by the formula wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, and R means an arylresidue of the benzene or naphthalene series, which may contain further substituents, which dyestuffs are when dry dark blue to green powders, soluble in concentrated sulfuric acid to an olive, green to blue solution, and dye cotton and wool in a yellow, red to brown vat fast blue to green shades, which dyestuffs may be obtained by condensing perinaphthoxypenthiophenes of the general formula:

X X wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a lnonovalent substituent, with a-isatin compounds of the general formula:

wherein R is an arylresidue of the benzene or naphthalene series, which may contain further substituents, R, a halogen or an arylidogroup.

2. ,As: new products-vat dyestuffs ofthe 2ethionaphthene-Zindolindigo series, having: probably the general formula:

wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent', and R means a halogenized arylresidue of the benzene or naphthalene series, which may contain further substituents, which dyestuifs'are when dry dark blue to'green, powders, soluble in concentrated sulfuric acid to an olive, green to blue solution, and dye cotton and wool in a yellow, red'to brown vat fast blue togreen shades, which-dyestuffs may be obtainedby condensing] perinaphthoxypenthiophenes' of the general formula wherein the Xs stand forv hydrogen atoms, of which one or more may be replaced by a moncvalent substituent, with a-isatin compounds of the general formula i NH-Y wherein the his stand for'hyd'i'ogen atoms,

of which one or more may be replaced by a monovalent substituent, Y means hydrogen, which may be'substitutedaby an acylgroup,

,R a halogenized'arylresidue of the benzene or naphthalene series, which may contain further substituents, which. dyestuffs are,

whendry, dark blue to green powders, soluble in concentrated sulfuric acid'to an olive, green to blue solution, and dye cotton andl wool in a yellow, red to brown vat fast blue to green shades, whichdyestufi's may beiozbe tained by condensing perinaphthoXypenthie ophenes of the general formula:

wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, Y is hydrogen, which may be substituted by an acylgroup, with or-lStltlI] compounds of the generalformula:

wherein R is a halogenized arylresidue of the benzene or. naphthalene series, which may contain further substituents, R, a halo gen 01" an arylidogroup;

a; As new products vat dyestufls of the 2-thionaphthene 2-ind'olindigo series, having probably the general formula:

L. alogcn wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, which dyestufi's are, when dry, dark blue to green powders, soluble inconcentrated sulfuric acid to an olive, green to blue solution, and dye cotton andwool in a yellow, red to brown vatfa-st blue to green" shades, which dyestuffs may be obtained by condensing perinaphthoxypenthiophenes of the general formulaz wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, with a-1-acyl-2.3- naphthisatin compounds of the formula:

'-' alogen wherein R is a halogen or an arylidogroup.

5. As new products Vat dyestuffs of the 2-thionaphthene-2-indolindigo series, having probably the formula:

wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, and Y means an acylgroup, which dyestuffs are, when dry,

dark green powders, soluble in concentrated sulfuric acid to an olive-green solution, and dye cotton and wool in a red vat fast pure green shades, which dyestufis may be obtained by condensing Q-acyl-aminoperinaphthoxypenthiophenes of the formula:

wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent and Y is an acylgroup, with an a-I-haIogen-Q.3-naphthisatin compound of the formula:

CO 5 R1 6 8 7 N (1) slogan wherein R is a halogen or an arylidogroup.

6. As new products vat dyestuffs of the 2-th1onaphthene-Q-indolindigo series, having probably the formula:

d z X s 8 o 4 o=oz 5 s 6 2t 4 1 s 7 H z x 2;

wherein the Xs stand for hydrogen atoms, of which one or more may be replaced by a monovalent substituent, with an a-isatin compound of the formula:

wherein the Zs stand for hydrogen or other monovalent substituents and of which two or more may be replaced by halogens, and R is a halogen or an arylidogroup.

In testimony whereof, we afiix our signatures.

RICHARD HERZ. TENS R. 

